EP0255983B1 - Farbphotoempfindliches Silberhalogenidmaterial für schnelle Behandlung - Google Patents

Farbphotoempfindliches Silberhalogenidmaterial für schnelle Behandlung Download PDF

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Publication number
EP0255983B1
EP0255983B1 EP87306813A EP87306813A EP0255983B1 EP 0255983 B1 EP0255983 B1 EP 0255983B1 EP 87306813 A EP87306813 A EP 87306813A EP 87306813 A EP87306813 A EP 87306813A EP 0255983 B1 EP0255983 B1 EP 0255983B1
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EP
European Patent Office
Prior art keywords
silver halide
mol
silver
emulsion
halide emulsion
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EP87306813A
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English (en)
French (fr)
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EP0255983A3 (en
EP0255983A2 (de
Inventor
Keiji Ohbayashi
Mitsuhiro Okumura
Takaaki Kojima
Shigeo Tanaka
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Konica Minolta Inc
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Konica Minolta Inc
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Priority claimed from JP61300107A external-priority patent/JPH0693079B2/ja
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Publication of EP0255983A3 publication Critical patent/EP0255983A3/en
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    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/10—Organic substances
    • G03C1/12—Methine and polymethine dyes
    • G03C1/14—Methine and polymethine dyes with an odd number of CH groups
    • G03C1/16—Methine and polymethine dyes with an odd number of CH groups with one CH group
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C1/00—Photosensitive materials
    • G03C1/005—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein
    • G03C1/06—Silver halide emulsions; Preparation thereof; Physical treatment thereof; Incorporation of additives therein with non-macromolecular additives
    • G03C1/08—Sensitivity-increasing substances
    • G03C1/09—Noble metals or mercury; Salts or compounds thereof; Sulfur, selenium or tellurium, or compounds thereof, e.g. for chemical sensitising
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03C—PHOTOSENSITIVE MATERIALS FOR PHOTOGRAPHIC PURPOSES; PHOTOGRAPHIC PROCESSES, e.g. CINE, X-RAY, COLOUR, STEREO-PHOTOGRAPHIC PROCESSES; AUXILIARY PROCESSES IN PHOTOGRAPHY
    • G03C7/00—Multicolour photographic processes or agents therefor; Regeneration of such processing agents; Photosensitive materials for multicolour processes
    • G03C7/30—Colour processes using colour-coupling substances; Materials therefor; Preparing or processing such materials
    • G03C7/392—Additives

Definitions

  • the present invention relates to a process for the preparation of a silver halide color photosensitive material and, more particularly, to a process for the preparation of a rapidly processable silver halide color photosensitive material having a silver halide emulsion layer composed principally of silver chloride and which is able to produce a satisfactory dye image when rapidly processed.
  • the rate of development in the process of color development is subject to the effects of two sources.
  • One of the sources is the silver halide color photosensitive material used and the other is the color developing solution used.
  • the particle shape and size in and the composition of the photosensitive silver halide emulsion used have considerable bearing on the rate of development
  • the rate of development is likely to be influenced by the conditions of the color developing solution and, more particularly, by the type of development restrainer used, and that grains which contain a high concentration of silver chloride in particular exhibit a remarkably high development rate under specific conditions, for example, such that bromide ions conventionally used for color development are not contained in the color developing solution.
  • a blue-sensitive emulsion layer is normally present as the lowermost layer, and therefore the emulsion layer is required to contain silver halide grains which show high sensitivity and a high rate of development.
  • a method for increasing the rate of development is known in which a combination of a silver halide and a low-bromide silver is used, as disclosed in JP-A-58-184142 and JP-B-56-18939.
  • the difficulty with methods in which the silver chloride content of the emulsion layer is increased is that the photosensitivity is inevitably lowered. This is attributable to the fact that pure silver chloride absorbs almost no visible light by nature.
  • a spectral sensitizing dye in the form of a cyanine dye having two benzothiazole rings in a molecule can enhance spectral sensitization in the visible light range, and more particularly in the light range of 430 nm - 480 nm, thereby providing sufficient sensitivity even where a high-purity silver chloride is used.
  • the difficulty is that if the high-purity silver chloride is used in combination with such spectral sensitizing dye, a downward change in gradation will take place where development is effected with a color developing solution using a p-phenylenediamine of the type which is normally used for the purpose of development, so that it is not possible to obtain satisfactory color reproduction.
  • Another difficulty is that where a developing solution having little or no bromide content is used with a view to increasing the rate of development, far much greater deterioration in gradation will result.
  • US Patent No. 4 225 666 discloses a method of preparing a spectrally sensitized radiation-sensitive silver chloride emulsion comprising the addition of a methine spectral sensitizing dye to an aqueous solution of a silver salt, an aqueous solution of a halide salt and a peptizer.
  • the sensitizing dye is incorporated in the silver halide emulsion before the end of the first ripening stage which corresponds to the precipitation of the silver halide.
  • This invention is intended to overcome the aforesaid difficulties, and seeks to provide a process for the preparation of a silver halide color photosensitive material with a high silver chloride content and yet is able to prevent the development of any excessive decrease in gradation with a dye image produced from the material, and which, even when a color developing solution having no benzyl alcohol content is used, can assure a sufficient maximum density and formation of a satisfactory dye image at a very high rate of development.
  • the invention provides a process for the preparation of a silver halide color photographic light sensitive material comprising a support having thereon at least one photographic component layer including at least one silver halide emulsion layer comprising:
  • silver halide grains containing not less than 80 mol% of silver chloride, the gold compound, sulfur sensitizer, and the compound expressed by formula [I] are all contained in one silver-halide emulsion layer (which is hereinafter sometimes referred to as the "silver halide emulsion layer used in the invention"), if the photosensitive material in accordance with the invention has only one such emulsion layer. If the photosensitive material has a plurality of silver-halide emulsion layers, at least one of the layers should be the silver halide emulsion layer used in the invention.
  • a blue sensitive emulsion layer which is usually formed as the lowermost layer (i.e., the layer nearest to the base) has the aforesaid compositional features of the invention so that it constitutes the silver halide emulsion layer used in the invention.
  • a yellow coupler contained in the blue sensitive emulsion layer is selected from the couplers represented by the general formula [Y] mentioned hereinafter.
  • the photosensitive material has a plurality of silver halide emulsion layers some of those layers need not be of the same composition as the silver halide emulsion layer used in the invention.
  • Gold compounds useful for incorporation in the silver halide emulsion layer include, for example, aurate chloride, sodium chloroaurate, and potassium thiosulfo-aurate (but without limitation thereto).
  • the proportion of such gold compound used is 5 x 10 ⁇ 7 to 5 x 10 ⁇ 3 mol per mol of the silver halide, preferably 1.0 x 10 ⁇ 6 to 1 x 10 ⁇ 4 mol. More preferably, it is 1.0 x 10 ⁇ 6 to 4 x 10 ⁇ 5, most preferably 1.0 x 10 ⁇ 6 to 9 x 10 ⁇ 6.
  • the gold compound may be added at any stage in the process of silver halide emulsion preparation, but preferably between the end of the stage of silver halide formation and the end of the stage of chemical sensitization. Alternatively, it may be added after the end of the stage of chemical ripening, or more particularly after the addition of a compound known as an antifoggant or stabilizer and before the stage of silver halide emulsion coating. In other words, the gold compound is effective even when added at any time other than at a usual time for gold sensitization, that is, at any time at which it cannot exhibit its sensitizing effect.
  • Sulfur sensitizers useful for incorporation in the silver halide emulsion layer used in the invention include, for example, sodium thiosulfate, and thiourea derivatives such as diphenyl thiourea and allyl thiourea.
  • a sulfur sensitizer may be added in such quantity as is sufficient to sensitize the silver halide.
  • the quantity of sulfur sentizer but where sodium thiosulfate is used, it is added preferably at the rate of from 1 x 10 ⁇ 7 to 1 x 10 ⁇ 5 mol per mol silver halide, more preferably at the rate of from 2 x 10 ⁇ 6 to 8 x 10 ⁇ 6 mol per mol silver halide.
  • X1, X2, X3, and X4 represent hydrogen, halogen, alkyl, alkoxy, aryl, or hydroxy. More specifically, a halogen may be, for example, chlorine.
  • Alkyl groups may be, for example, methyl or ethyl having from 1 to 6 carbon atoms.
  • Alkoxy groups may be methoxy or ethoxy having from 1 to 6 carbon atoms.
  • at least one of X1, X2, X3 and X4 is chlorine, and more preferably two of X1, X2, X3 and X4 are chlorine.
  • R1 and R2 represent optionally substituted alkyl.
  • R1 and R2 are unsubstituted alkyl, or carboxyl- or sulfo-substituted alkyl, more preferably carboxyl- or sulfo-substituted alkyl. Most preferably, they are sulfo-alkyl or carboxy-alkyl having from 1 to 4 carbon atoms.
  • R1 and R2 may be identical with or different from each other.
  • one of them is a carboxyl-substituted alkyl group having 1 to 4 carbon atoms.
  • X ⁇ represents an anion. Though not definitive, it may be a halogen ion (such as Br ⁇ or I ⁇ ). n represents 0 or 1.
  • Spectral sensitizing dyes of formula [I] are individually known compounds, which may easily be synthesized by reference to various publications, such as for example the respective specifications of British Patent No. 660408, U.S. Patent No. 3149105, and JP-A-50-4127, as well as F.M. Hamer, "The Cyanine Dyes and Related Compounds", Interscience Publishers, New York, 1969, pp 32 - 76.
  • NEt3 represents
  • the proportion of any such spectral sensitizing dye as exemplified above, relative to silver halide is 5 x 10 ⁇ 6 - 5 x 10 ⁇ 2 mol/AgX mol.
  • the proportion is 1 x 10 ⁇ 5 - 1 x 10 ⁇ 3 mol/AgX mol.
  • it is 1 x 10 ⁇ 4 - 9 x 10 ⁇ 4 mol/AgX mol.
  • the spectral sensitizing dye may be added to an emulsion of silver halide according to any relevant technique well known in the art.
  • the sensitizing dye may be dispersed directly in the emulsion, or may be added to the emulsion in the form of an aqueous solution or a solution prepared by dissolving the dye in a water soluble solvent, such as pyridine, methyl alcohol, ethyl alcohol, methyl Cellosolve, or acetone (or a mixture of any such solvents), or in the form of a solution of the dye diluted with water.
  • Ultrasonic vibration may be advantageously used in connection with the dissolving step.
  • a single spectral sensitizing dye expressed by formula [I] may be used alone for the purpose of the invention, or two or more of such dyes may be used in combination. Where two or more of such dyes are used, they may be added either simultaneously or separately. If they are added separately, the sequence, timing, and intervals for the addition may be determined according to the intended object. If so desired, such dye may be used in combination with a sensitizing dye other than those of formula [I].
  • the sensitizing dye may be added to the silver halide photosensitive emulsion in parts.
  • the silver halide emulsion used in the formation of the silver halide emulsion layer used in the invention may be of silver chlorobromide, silver iodochloride, or silver chloroiodobromide silver chloride, provided that it is a silver halide emulsion containing not less than 80 mol% of silver chloride.
  • the emulsion contains silver chloride in an amount of from 95 to 100 mol%, and more preferably, of from 99.0 to 99.9 mol%.
  • the emulsion may contain silver iodide but the content of silver iodide is preferably not more than 1 mol%, more preferably not more than 0.5 mol%. Most preferably, the emulsion contains no silver iodide.
  • the silver bromide content of the emulsion is preferably less than 5 mol%, or it may be even 0 mol%.
  • the silver halide grains containing not less than 80 mol% of silver chloride should preferably constitute not less than 80% by weight, more preferably 100% by weight, of the entire silver halide grain content of the silver halide emulsion layer in which the silver halide grains are contained. Further, the mean silver chloride content of the emulsion layer in which the silver halide grains are contained should preferably be not less than 80 mol%, more preferably not less than 85 mol%.
  • the silver halide grains contained in the silver halide emulsion layer should preferably have a mean silver halide content of not less than 80 mol%, which means that the molar ratio of silver chloride to the entire emulsion layer is not less than 80 mol%. It is permissible to have a partial deviation from said compositional feature of the grains, or the layer to contain some other substance (such as for example pure silver bromide) than the one represented by said molar ratio.
  • the photosensitive material prepared by a process according to the invention has a plurality of silver halide emulsion layers
  • some of the emulsion layers may be of a different composition from that of the silver halide emulsion layer used in the invention, and these other emulsion layers need not be of a high silver chlorohalide composition.
  • the emulsion layers, as a whole, of the photosensitive material preferably have a mean silver halide content of not less than 80 mol%, and more preferably all the emulsion layers contain silver halide grains having a silver chloride content of not less than 80 mol%. It is particularly desirable that all the layers have, on average, a silver chloride content of not less than 95 mol%.
  • Silver halide grains used in the color photosensitive material prepared in accordance with the invention namely, silver halide grains used in the silver halide emulsion layer and other emulsion layer or layers which may be formed as required (hereinafter referred to as "silver halide grains used in the invention") preferably have a mean grain size of less than 5 ⁇ m, more preferably less than 3 ⁇ m, and most preferably less than 1 ⁇ m, in terms of mean grain diameter as defined by the following equation: in which r represents mean grain diameter; r i represents individual grain diameter; and n i represents the number of particles having individual grain diameter r i .
  • the length of one side of the cube is taken as the diameter of each individual grain; and if the grains are spherical or of any shape other than cubic, the length of one side of a cube having same volume is taken as the diameter of each individual grain.
  • the grain diameter distribution of the silver halide grains used in the invention may be of a polydisperse pattern or of a monodisperse pattern, but it is desirable that the silver halide emulsion should be monodisperse.
  • monodisperse herein means that the coefficient of variation of the grain diameter distribution of silver halide grains contained in the emulsion is not more than 22%, preferably not more than 15%. The coefficient of variation indicates the spread of grain diameter distribution and is defined by the following equation:
  • the grain diameter can be measured by various methods conventionally used in the art for the above mentioned purpose.
  • a typical method is described in Lapland "Method of Grain Diameter Analysis", A.S.T.M. Symposium on Light Microscopy, 1955, pp 94 - 122.
  • Another typical method is described in "The Theory of Photographic Process", Mees and James, 3rd ed., The Macmillan Press Ltd (1966), Chap. 2.
  • silver halide emulsion refers to an emulsion constituting the silver halide emulsion layer used in the invention and any emulsion constituting any other emulsion layer which may be formed as required.
  • Silver halide grains used for this purpose may be produced by the acid process, the neutral process, or the ammonia process, for example. The grains may be grown all at once, or seed grains may be prepared initially which are then grown. The technique for seed grain preparation may be the same as or different from the technique for grain growing.
  • the silver halide emulsion may be prepared by mixing together an halide ion and a silver ion, or by mixing one into a liquid in which the other is present.
  • the halide ion and the silver ion may be gradually added together in a mixing vessel while the pH and pAg in the vessel are properly controlled paying attention to the critical rate of growth of silver halide crystals so that they are grown into a silver halide emulsion.
  • the grains may be varied in their halogen composition by using a conversion technique.
  • any appropriate apparatus can be used to prepare the silver halide emulsion. More particularly, apparatuses utilizing any one of the following methods can be advantageously employed. In one such method an aqueous silver halide solution and an aqueous solution of salt halide are introduced through nozzles immersed in a hydrophilic colloidal solution in a mixture pot. In another method the concentration of an addition liquid is successively varied. In another method excess quantities of soluble salt and water in a hydrophilic colloidal solution in the mixing vessel are removed, for example, by ultrafiltration in order to prevent interparticle intervals from becoming larger.
  • the size and shape of silver halide grains, their grain size distribution, and the rate or their growth can be suitably controlled by using a silver halide solvent as required.
  • a metallic ion selected from a cadmium salt, a zinc salt, a lead salt, a thallium salt, an iridium salt (present as a complex salt), a rhodium salt (present as a complex salt), or a ferric salt (present as a complex salt) may be added to the silver halide grains during grain formation and/or grain growth.
  • the resulting grains contain the metallic element in their interior and/or on their surface, or may have a reduction sensitivity speck in their interior and/or on their surface when placed in a reductive atmosphere.
  • the silver halide emulsion used in the invention may be cleared of all unnecessary soluble salts at the end of the stage of silver halide grain growth, or may be allowed to contain such salts as they are.
  • the method described in "Research Disclosure" No. 17643 may be employed.
  • Silver halide grains used in the silver halide emulsion may be either those having a uniform silver halide distribution within their interior or core/shell grains having silver halide compositions that differ between their interior and their surface.
  • Silver halide grains in a silver halide emulsion having a high chloride content are likely to have a cubic shape.
  • a regular crystal shape as, for example, a cube, octahedron, or a quaterdecahedron.
  • they may have an irregular configuration, for example, spherical or lamellar.
  • These grains may have any desired side-to-side ratio.
  • they may have a composite form of these crystalline shapes, or they may be a mixture of grains having different crystalline shapes. In the present invention, however, cubic grains are preferably used.
  • the silver halide emulsion used in the invention may be a mixture of two or more kinds of silver halide emulsions which have been prepared separately.
  • the silver halide color photographic light sensitive material of the invention may preferably contain a black-and-white developing agent in one of the photographic structural layers.
  • black-and-white developing agents which may be used in the invention is not specifically limited and includes those widely used in the photographic art. Specifically, however, the preferred agents include triazole-3-pyrazolidone compounds, di- or poly-hydroxybenzene compounds and N-alkyl-p-aminophenol compounds.
  • Typical examples of black-and-white developing agents usable in connection with the present invention are as follows.
  • the agent may be added either unchanged or after being dissolved in an appropriate solvent such as water or alcohol (which does not exert adverse effects on the light-sensitive material) at an appropriate proportion to the coating solutions to form the layers.
  • the black-and-white developing agent may be incorporated into the layers after being dissolved in high boiling and/or low boiling organic solvents and then dispersing and emulsifying the solvents into water.
  • high boiling solvents i.e. those having boiling points higher than 150°C
  • examples of high boiling solvents are as follows: phenol derivatives, alkyl phthalates, phosphates, citrates, benzoates, alkylamides, fatty acyl esters, and trimesyl esters, each of which does not react with the oxidized product of the developing agent.
  • Low boiling or water soluble organic solvents which may be used together with or instead of the high boiling solvents are described in, for example, U.S. Patents No. 2,801,171 and No. 2,949,360.
  • Examples of low boiling organic solvent are as follows:
  • the black-and-white developing agent may be added at any step during the manufacturing process, but it is generally favorable to add the agent to the emulsion immediately before it is applied.
  • the black-and-white developing agent may be a combination of more than two agents.
  • the black-and-white developing agent may be contained in any of the photographic component layers; however, it is advantageous to incorporate the agent into the silver halide emulsion layers or adjacent layers thereto.
  • the amount of developing agent added depends on the type of agent and the silver halide, but ordinarily, 0.1 - 100 mg, or favorably 0.5 - 10 mg, per m2 is added.
  • the sensitizing dye represented by formula [I] and the black-and-white developing agent may be contained in a same layer or in different layers.
  • the light sensitive material of the invention may contain a dye-forming coupler capable of forming a dye by coupling with the oxidized product of an aromatic primary amine developing agent (such as, for example, p-phenylenediamine derivative and aminophenol derivative) during color developing.
  • an aromatic primary amine developing agent such as, for example, p-phenylenediamine derivative and aminophenol derivative
  • Such couplers may be contained in any of the emulsion layers of the light sensitive material. However, as mentioned previously, the yellow coupler should favorably be contained within the silver halide emulsion layer. Yellow couplers suitable for use in the process of the invention are described in, for example, the following patents : U.S. Patents No. 2,186,849, No. 2,322,027, No. 2,728,658, No. 2,875,057, No. 3,265,506, No. 3,277,155, No. 3,408,194, No. 3,415,652, No. 3,447,928, No. 3,664,841, No. 3,770,446, No. 3,778,277, No. 3,849,140 and No.
  • Examples of particularly favorable yellow couplers include those of formula [Y] below.
  • yellow couplers which are advantageously used in the color photographic light sensitive material are divalent, non-diffusible yellow couplers of formula [Y]: wherein R21 is halogen or alkoxy; R22 is -NHCOR23SO2R24, -COOR24, -COOR23COOR24, or in which R23 is alkylene, R24 is a ballast group and R25 is alkyl, aralkyl or hydrogen; and Z21 is a group capable of being split off in a reaction with an oxidized product of a color developing agent.
  • the yellow couplers above are typically used at a rate of 0.02 - 1 mol, favorably, 0.05 - 0.75 mol, more favorably, 0.05 - 0.75 mol, and most favorably 0.1 - 0.5 mol per mol silver halide.
  • the yellow couplers above may be used as a mixture comprising, at an arbitrarily selected ratio, more than two similar couplers.
  • Magenta couplers suitable for use include, for example, those mentioned in the respective specifications of U.S. Patent Nos. 1,969,479, 2,213,986, 2,294,909, 3,338,677, 2,340,763, 2,343,703, 2,359,332, 2,411,951, 2,435,550, 2,592,303, 2,600,788, 2,618,641, 2,619,419, 2,673,801, 2,691,659, 2,803,554, 2,829,975, 2,866,706, 2,881,167, 2,895,826, 3,026,653, 3,127,269, 3,214,437, 3,253,924, 3,311,476, 3,419,391, 3,486,894, 3,519,429, 3,558,318, 3,617,291, 3,684,514, 3,705,896, 3,725,067, and 3,888,680, British Patent Nos.
  • Cyan couplers suitable for use include, for example, those mentioned in the respective specifications of U.S. Patent Nos. 2,306,410, 2,356,475, 2,362,598, 2,367,531, 2,369.929, 2,423,730, 2,474,293, 2,476,008, 2,498,466, 2,545,687, 2,728,660, 2,772,162, 2,895,826, 2,976,146, 3,002,836, 3,419,390, 3,446,622, 3,476,563, 3,737,316, 3,758,308, and 3,839,044, Britich Patents Nos.
  • Couplers capable of forming a coupling product having a maximal spectral absorption wavelength in a wavelength region of 700nm to 850nm are mentioned in Japanese Published Examined patent Application No. 52-24849, and Japanese Published Unexamined Patent Application Nos. 53-125836, 53-129036, 55-21094, 55-21095, and 55-21096.
  • the coupler may be incorporated into a silver halide emulsion by using a high boiling point organic solvent and a dispersing agent.
  • Various compounds may be contained in the silver halide photosensitive material of the invention in order to inhibit fogging during manufacture or storing, or in the process of development, or to stabilize the photographic performance of the material.
  • any of the following may be added: tetrazinedenes, azoles, such as benzothiazolium salts, nitroindazoles, nitrobenzoimidazoles, chlorobenzoimidazoles, bromobenzoimidazoles, memercaptothiazoles, mercaptobenzoimidazoles, aminotriazoles, benzotriazoles, nitrobenzotriazoles, mercaptotetrazoles (more specifically, 1-phenyl-5-mercaptotetrazole); mercaptopyrimidines, mercaptotriazines including oxazolithione and similar compounds; and various other compounds known as antifoggants or stabilizers, such as benzene thiosulfonic acid, benzenesulfonic acid, benzenesulfonamide, hydroquinone derivatives, aminophenol derivatives, gallic acid derivatives, and ascorbic acid derivatives.
  • azoles such as benzothiazolium
  • Hydrophilic colloids useful for forming a hydrophilic colloidal layer in the silver halide photosensitive material of the invention are not particularly limited.
  • gelatin and various other colloids may be used as binders for photosensitive and nonphotosensitive layers as required.
  • the following may be used; colloidal albumin, agar-agar, gum arabic, dextrin, alginic acid, cellulose derivative, such as a cellulose acetate hydrolyzed to an acetyl content of 19 - 26%, for example, polyacrylamide, imidized polyacrylamide, casein, urethane carboxylic acid group, such as vinylalcohol-vinyl cyanoacetate copolymer or vinylalcohol copolymer containing a cyanoacetyl group, polyvinylalcohol-polyvinylpyrolidone, hydrolyzed polyvinyl acetate, a polymer produced by polymerization of a protein or a saturated protein acylate with a mono
  • Any suitable compound may be used as a hardening agent.
  • organic hardening agents such as vinylsulfone, hardeners containing an acryloyl group, or ethylene imine and/or inorganic hardening agents such as chrome alum or potassium alum, or a combination of two or more agents may be used.
  • the photosensitive material of the invention may contain a surface active agent for coat assisting, antistatic, emulsion dispersing, slip facilitating, emulsion dispersing, and adhesion inhibiting purposes, for example.
  • Surface active agents useful for these purposes include, for example, saponin, sodium dodecylbenzene sulfonate, sodium sulfosuccinate, and also those mentioned in JP-A-49-46733, 49-10722, and 50-16525.
  • a ultraviolet light absorber it is possible to use compounds such as benzotriazoles, thiazolidones, acrylonitriles and benzophenones.
  • antistatic, optical bleaching, antioxidant, and stainproofing agents may be used as required.
  • a photographic additive is incorporated into the silver halide emulsion, and then a silver halide emulsion layer is formed on a base.
  • a subbing layer and an intermediate layer may be formed between the base and the silver halide emulsion layer.
  • Materials useful for the base include, for example, paper, glass, cellulose acetate, cellulose nitrate, polyester, polyamide, and polystyrene. Bonded materials consisting of a laminate of two or more kinds of base materials, such as, for example, paper and olefin (e.g., polyethylene or polypropylene), may also be used.
  • the base material is generally subjected to various sorts of surface treatment, such as electron bombardment treatment and subbing treatment for the formation of a subbing layer.
  • a generally known coating method such as dip coating, roller coating, bead coating, or curtain flow coating, is employed. Coating is followed by drying.
  • the photosensitive material may be developed by a conventional color development process.
  • Color developing agents useful for color development inculde aromatic primary amine compounds such as, for example, N-diethyl-p-phenylene diamine, N-ethyl-N-hydroxyethyl paraphenylene diamine, 4-(N-ethyl-N-hydroxyethyl) amino-2-methylaniline, 4-(N-ethyl-N- ⁇ -methanesulfone amide ethyl) amino-2-methylaniline, 4-(N, N-diethyl) amino-2-methylaniline, and 4-(N-ethyl-N- methoxyethyl) amino-2-methylaniline, and their sulfates, hydrochlorides, sulfites, and p-toluene sulfonates.
  • a rapid color developer in particular may contain various developer additives in addition to aforesaid color developing agent and an N, N-dialkyl hydroxylamine salt as a preserver.
  • alkaline agents such as sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium metaborate, and tribasic potassium phosphate
  • pH buffers such as sodium phosphate, potassium dihydrogen phosphate, sodium dihydrogen phosphate, and potassium bicarbonate
  • organic solvents such as methanol, ethyleneglycol, and triethanolamine
  • the color developing solution may contain benzyl alcohol as a color improver, but preferably it contains no such agent.
  • the solution may contain a small amount of a color improver.
  • the amount of benzyl alcohol in the color developing solution is preferably 0 to 5 ml per liter of the solution, more preferably 0 to 3 ml.
  • sulfites such as sodium sulfite and potassium sulfite, in combination with N, N-dialkylhydroxylamine in the solution.
  • the sulfite is used preferably in the proportion of 0.05 g to 12 g per liter of the solution, more preferably 0.1 g to 0.3 g.
  • a water-soluble bromide is contained as a development restrainer in the color developing solution, it should preferably be present in a minimal amount.
  • the solution may contain a small amount of bromide, but most preferably it contains no bromide.
  • rapid processing generally means that the time taken for color development is less than 90 seconds.
  • the temperature of the color developing solution is generally within the range of 20°C to 50 °C, preferably 30 °C to 40 °C.
  • the time for bleach-fixing is preferably less than 90 seconds, more preferably less than 60 seconds.
  • Preferred bleaching agents for developed silver are polymetallic salts of organic acids.
  • polymetallic salts are ferric salts of organic acids for example, ferric salts of nitrilotriacetic acid, diethylenetriaminepentaacetic acid, ethyleneglycol-bis (aminoethylether) tetraacetic acid, diaminopropanoltetraacetic acid, N-(2-hydroxyethyl) ethylenediaminetriacetic acid, ethyliminodipropionic acid, cyclohexanediaminetetraacetic acid, or ethylenediaminetetraacetic acid.
  • Ferric salts of polycarboxylic acids as mentioned in JP-A-49-107737 may also be used, which include, for example, salts of oxalic acid, malonic acid, succinic acid, tartaric acid, malic acid, tartaric acid, citric acid, and salicylic acid.
  • polymetallic salts useful for the purpose of the invention are cupric salts and cobalt (II) salts in addition to aforesaid ferric salts.
  • inorganic polymetallic acids such as ferric chloride and ferric sulfate, may be used depending upon the intended object.
  • known agents such as thiosulfate and thiocyanate, may be contained in the solution.
  • water soluble alkaline metallic salts or bromides or iodides of ammonium, may be used as described in JP-A-48-101934, which mentioneds potassium bromide, ammonium bromide, sodium iodide for this purpose.
  • a silver halide emulsion composed of silver chlorobromide grains having a mean grain diameter of 0.6 ⁇ m and a uniform silver chloride content of 10 mol% [Em-I] was prepared by a simultaneous mixing method.
  • a silver halide emulsion composed of silver chlorobromide grains having a mean grain diameter of 0.6 ⁇ m and uniformly containing 3 mol% of silver bromide [Em-2] was prepared by same mixing method.
  • Sensitivity values in Table 1 refer to relative sensitivity values and correspond to values calculated relative to the sensitivity in the color development of sample No. 105 under processing mode A which is taken as 100.
  • Color Developing Solution A B Pure water 800 ml 800 ml Ethylene glycol 15 ml - Benzyl alcohol 15 ml - N, N-diethylhydroxylamine - 6 ml Potassium chloride 2.0 g 2.0 g Potassium brimide 0.8 g - Potassium sulfite 2 g 0.2 g N-ethyl-N- ⁇ -metasulfoneamide ethyl-3-methyl-4-amino aniline sulfate 5 g 5 g Tetrasodium polyphosphate 2 g 2 g Potassium carbonate 30 g 30 g Triethanolamine - 8.3 g Distilled water was added until the quantity of the solution reached 1 l.
  • test piece Nos. 101 - 108 using Em-1 emulsion having a high silver bromide content those in which reference spectral sensitizing dyes A, B, C were used (sample Nos. 101 - 103) showed low sensitivity values, but those using spectral sensitizing dyes of formula [I] (sample Nos. 104 - 108) showed high sensitivity values. In the latter mentioned cases, the ⁇ 1, ⁇ 2 values showed satisfactory gradation. However, the results of 45 s rapid processing (in the present instance, a developing solution containing no benzyl alcohol was used) show that sensitivity values decreased further with sample Nos 101 - 103, and those of sample Nos. 104 - 108 also dropped noticeably.
  • test piece Nos. 112 - 117 using emulsion Em-2 with spectral sensitizing dyes of formula [I] it is clear from the 3 min processing data that fairly high sensitivity values were obtained, but they showed much lower gradation than those containing reference sensitizing dyes (sample Nos. 109 - 111). Results of 45 s processing showed that their ⁇ 1, ⁇ 2 values were lower than those of test piece Nos. 109 - 111, which means softer gradation.
  • Sample Nos. 118 and 119 used emulsion Em-2 containing reference sensitizing dye C and gold chloride. A comparison of these samples with sample No. 111 shows that the presence of the gold compound can give some improvement in ⁇ 1, ⁇ 2 thus producing a somewhat higher contrast. However, sensitivity remains low.
  • Sample Nos. 120 - 131 represent the present invention.
  • the test pieces of the invention have an advantage in the degree of improvement in ⁇ 1, ⁇ 2 values due to the presence of the gold compound.
  • the greater high contrast effect of the gold compound can be obtained when spectral sensitizing dyes of formula [I] are used.
  • the samples of the invention showed much higher sensitivity since they incorporated compounds of formula [I].
  • no soft gradation effect was seen with sample Nos. 120 - 131, and ⁇ 1, ⁇ 2 values of the test pieces in the case of 3 min processing compared well to those of sample Nos. 101 - 108 in 3 min processing.
  • the samples of the invention showed almost no change in either sensitivity or gradation, proving their suitability for rapid processing.
  • the photosensitive material of the invention is rapidly processable, highly sensitive, and is free from gradation lowering.
  • Sample No. 132 has a larger amount of gold compound than specified by the invention.
  • the test results show that it is less sensitive and produces excessively high contrast gradation. Therefore, it cannot provide any satisfactory image.
  • Sample No. 133 shows the opposite case, that is, it has an excessively small amount of gold compound. The image obtained is of excessively low gradation.
  • Samples were prepared which were same as sample Nos. 120, 127 using emulsion Em-2 in Example 1 except that yellow coupler CY-1 was used instead of yellow coupler Y-1 in samples 120, 127.
  • the samples so prepared were referred to as samples 201, 202.
  • color development was carried out using color developing solution P-2 (which did not contain benzyl alcohol) and another color development solution comprising 15 ml of benzyl alcohol added to the ingredients of developer A respectively.
  • Reflective maximum density (Dmax) was measured by employing the same densitomer as used in Example 1.
  • test pieces 203, 204 could give a higher color dye image density in a color developing solution in which BeOH was used.
  • samples 205 - 209 yellow couplers Y-4, Y-39, Y-6, Y-43 or Y-43 were each substituted for yellow coupler (Y-1) in sample 204 (sample 127 in Example 1).
  • a tendency similar to the one observed with samples 203, 204 was seen with samples 205 - 209.
  • Ripening was carried out with emulsion Em-2 by using the sodium thiosulfate in Table 3. Then, 3 x 10 ⁇ 4 mol/Ag mol of the spectral sensitizing dye [I-1] was added. Successively thereafter, a gold compound (e.g., gold chloride) was added in such amount as shown in Table 3 and the emulsion was subjected to ripening for 10 min. An antifoggant and a stabilizer were added. The same coupler as used in Example 1 was then added, and sample Nos. 301 - 305 in Table 3 were thus prepared. After subjected to exposure, the test pieces were processed for development with (B) developing solution (containing neither benzyl alcohol nor potassium bromide).
  • B developing solution
  • any gold compound used in the invention if not subjected to ripening in conjunction with a yellow sensitizer, can produce the same effect as was observed in Example 1 by being added to the emulsion in such amount as specified by the invention. Apparently the presence of such an amount of gold compound serves to positively compensate the negative effect on gradation of the developing solution which contains no potassium bromide or BeOH (sample Nos. 302 and 303).
  • Dye [I] was used in same way as in sample 302 in Example 3, except that proportions of the dye were varied as shown in Table 4.
  • Chemical sensitization was optimized by maintaining each silver halide emulsion at 60 °C and adding 1.5 mg thiosulfate and 3 mg sodium chloroaurate per mol silver. Then, using the spectral sensitizing dyes listed in Table 5, spectral sensitization was effected, whereby 4-hydroxy-6-methyl-1,3,3a;7-tetrazaindene serving as a stabilizer was added into each emulsion at a rate of one g per mol silver halide.
  • DNP dinonylphthalate
  • HQ-1 2,5-dioctylhydroquinone
  • composition of each processing solution is as follows: Color developer: Pure water 800 ml N, N-diethylhydroxylamine 2 ml Potassium chloride 2 g Potassium sulfite 0.2 g N-Ethyl-N- ⁇ -methanesulfonamidethyl-3-methyl-4-aminoaniline sulfate 5 g Sodium tetrapolyphosphate 2 g Potassium carbonate 30 g
  • Pure water was added to the above ingredients to prepare 1 l of the solution, which was treated with sulfuric acid or potassium hydroxide to adjust the pH to 7.0.
  • a color developer was prepared by adding 0.3 ml-0.6 ml of the bleach-fixer per liter of the above color developer.
  • the amount of addition is represented as the amount of contaminant, and the amount in fact corresponds to the degree of contamination of the developer solution by bleach-fixer in practical processing, whereby the sensitometry was exercised on each of the similarly treated samples in order to determine the sensitivity, gradation, and fog of blue-sensitive emulsion layer.
  • each of the samples Nos. 507, 510 and 513 indicates high fog and large ⁇ when the developer is contaminated.
  • Example 5 Samples of Example 5 were allowed to stand for five days under the conditions of 50 °C and 70% RH for forced deterioration. With each sample, treatment was identical to that of Example 5, except that the developing time was modified to 45 seconds or one minute 15 seconds instead of the contamination test conditions, so as to assess the shelf life of each sample. The results are listed in Table 7.
  • Table 7 illustrate that the samples No. 501 and No. 502, comparison samples, show significantly decreased sensitivities after the forced deterioration, and that the samples No. 503 through No. 507, though having high sensitivitties, had significantly decreased sensitivities after the forced deterioration.
  • each of the samples Nos. 508, 509, 511, 512, 514 and 515 is excellent; each featuring high sensitivity, low fog, and limited sensitivity loss even after the forced deterioration.
  • the comparison samples Nos. 507, 510 and 153 independently show high fog and low stability to the fluctuation in processing conditions: there is a difference between a postdeterioration sample treated for 45 seconds and a similar sample treated for one minute 15 seconds.
  • Example 5 With the obtained samples, a test identical to that of Example 5 was exercised. The test results are listed in Table 9. Sample Nos. 505 and No. 506 in Example 5 were used as comparison samples, listed as samples No. 716 and No. 717 in Table 9.
  • Table 9 illustrating this example also provides results similar to those of Example 5.
  • Example 6 With the samples No. 716 through No. 719 of this example, a test identical to that of Example 6 was exercised, and results similar to those of Example 6 were obtained.
  • Example 7 With the samples of Example 7, a bleach-fixer contamination test identical to that in Example 5, as well as a forced deterioration identical to that in Example 6 were exercised, whereby the sensitivity and gradation fluctuation were measured for each of the samples. The results measured were compared with the sensitometric values of other green-sensitive layers and red-sensitive layers. As a result, it was learned that in the samples containing the black-and-white developing agent various fluctuation factors were improved, the sensitivity and gradation of the blue sensitive layer matching those of the other layers well.
  • Example 6 two samples were prepared in the same manner as in Example 5 except that the black-and-white agent was replaced. One sample was developed immediately after being prepared, and the other was stored for 5 days under the conditions of 50 °C and 70% RH, then exposed and developed. The effect of the present invention that the characteristic fluctuation after being forcedly deteriorated was small was proved as shown in Table 10. In addition, it was also proved that hydroxybenzene derivatives were effective in suppressing fogging.
  • silver chloro-bromide emulsion Em-13 containing 0.5 mol of silver bromide was prepared using the same manner as that used to prepare Em-12.
  • the average grain size of the emulsion obtained was 0.65 ⁇ m and the crystalline shape was cubic.
  • silver chloro-bromide emulsion Em-12 containing 2.5 mol of silver bromide was prepared using the same manner as that used to prepare Em-14.
  • the average grain size of the emulsion obtained was 0.65 ⁇ m and the crystalline shape was cubic.
  • Sodium thiosulfate was added as a sulfur sensitizing agent into emulsions Em-12 to Em-14 in an amount of 1 x 10 ⁇ 5 mol per mol of silver halide. Then 2 x 10 ⁇ 5 mol of chloroauric acid was added, then the obtained solution was chemically ripened.
  • Sensitizing dye I-22 shown above was added 5 min before the end of the ripening process in an amount of 10 ⁇ 4 mol per mol of silver halide, stabilizer ST-1 was added at the end of the ripening process in an amount of 10 ⁇ 3 mol per mol of silver halide, thus preparing a blue-sensitive silver halide emulsion.
  • the coating solution thus prepared was applied onto photographic support coated with polyethylene containing titanium oxide. Further, a protective layer was applied onto the support, thereby obtaining the samples.
  • the quantity of silver halide or gelatin contained in each layer applied was adjusted so that 0.4 g/m2 of metallic silver and 3.0 g/m2 of gelatin in the emulsion layer and 1 g/m2 of gelatin in the protective layer were obtained.
  • Bleach-fixer Pure water 800 ml Ammonium ferric (III) ethylenediaminetetraacetate 65 g Bisodium ethylenediaminetetraacetate 5 g Ammonium thiosulfate 85 g Sodium hydrogensulfine 10 g Sodium metabissulfite 2 g Sodium chloride 10 g N,N-diethylhydroxylamine (85% w:v solution) 2 ml Pure water was added to the above mixture to obtain one liter of solution, which was adjusted to pH 6.5 using dilute sulfuric acid.
  • the reflection density of the dye images obtained was measured using a PDA-65 densitometer (manufactured by Konishiroku Photo Industry Co., Ltd.) and using monochromatic blue light, thereby obtaining the results listed in Table 11.
  • the sensitivity is represented by a reciprocal of the exposure quantity which gives a density of 1.0, at the same time, by a relative value relative to the 100% sensitivity of Sample 1001.
  • Sample 1002 which employed the silver halide emulsion Em-13 containing 0.5 mol% of silver bromide, was of high-sensitivity and low in minimum density, and its maximum density was equivalent to that of the Em-12.
  • Em-15 and Em-16 were prepared in the same manner as that described for Em-12 in Example 10 but changing the amount of silver halide to 10 mol and 1000 mol respectively.
  • Em-17 and Em-18 were prepared in the same manner as that described for Em-13 but changing the amount of silver halide to 10 mol and 1000 mol respectively.
  • the average grain size of each emulsion was 0.65 ⁇ m and the crystalline shape was cubic.
  • Em-19 0.0025 l of a 2 mol/l potassium bromide solution was added instead of a 2 mol/l sodium chloride solution after adding 0.4975 l of silver nitrate solution, thereby obtaining silver chloro-bromide emulsion Em-19.
  • Em-20 and Em-21 were prepared in the same manner as that described above but changing the amount of silver halide to 10 mol and 1000 mol respectively.
  • the average grain size of the emulsion was 0.65 ⁇ m and the crystalline shape was cubic.
  • Each emulsion from Em-15 through Em-21 thus prepared was subjected to the chemical ripening, application, and characteristic evaluation steps in the same manner as described in Example 10. The results obtained are listed in Table 12.
  • the sensitivity of each sample is represented by a relative value relative to the 100% sensitivity of Sample 1101.
  • each silver halide emulsion obtained by preparation amount scale of 1 mol, 10 mol, and 1000 mol was exactly equivalent under the observation with an electron microscope.
  • the evaluation of photographic characteristics of each emulsion after chemical ripening step revealed that the sensitivity fluctuation of Em-13, 17, 18, 19, and 20, in which the contents of silver halide were within a range from 99.0 mol% through 99.5 mol%, was only approximately 3 to 4%.
  • Em-12, 15, and 16 showed a sensitivity fluctuation of approximately 6% and an increase in the minimum density.
  • a high sensitivity and a low minimum density in a silver halide color photographic light-sensitive material using an emulsion containing silver chloride from 99.0 to 99.5 mol% were reproduced in all samples irrespective of manufacturing lot.
  • silver bromide which is slightly effective in order to stabilize the photographic characteristics, is uniformly dispersed in the grain in an emulsion, in which silver bromide was formed at the final step for preparing the silver halide grain.
  • Samples were prepared in the same manner as that described in Example 10 except that the sensitizing dyes were replaced with the compounds listed in Table 13, and were subjected to the characteristic evaluation.
  • the sensitivity of each sample is represented by a relative value relative to the 100% sensitivity of Sample 1201.
  • the results shown in the table above reveal that the sensitizing dyes used in the present invention ensure a high sensitivity and a low minimum density by being combined with a silver halide emulsion containing a high content of chloride.
  • dyes such as I-27, I-34, I-45, and I-47 which contain an alkyl radical substituted with a sulfo radical and an alkyl radical substituted with a carboxyl radical, showed a low minimum density, thereby being preferable.
  • the sensitizing dye used in the present invention When the sensitizing dye used in the present invention is combined with the pure silver chloride emulsion Em-12, 15 or 16, the fluctuation in sensitivity caused by the preparation scale of the silver halide emulsion is apt to be larger than that when comparison dyes A or B are used. However, when the silver halide emulsion containing silver chloride from 99.0 to 99.5 mol% is used, the fluctuation is improved to the same level as that of comparison dye A or B. In addition, the features of a high sensitivity and a low minimum density are not lost.
  • comparison dyes C, D, or E having a naphthothiazole nucleus When comparison dyes C, D, or E having a naphthothiazole nucleus are used, a high sensitivity is obtained by comparison dye C or E.
  • the fluctuation in sensitivity caused by the preparation scale of the silver halide emulsion cannot be improved by combining Em-13, 17, or 18, which contain 0.5 mol% silver bromide.
  • comparison dye D is used, the sensitivity is low and the fluctuation in sensitivity cannot be improved.
  • the emulsion sensitized only by sulfur showed a low sensitivity and a large characteristic fluctuation, however, the sensitivity of emulsions is significantly improved and the characteristics are significantly stabilized by sensitizing with gold at the same time.
  • Silver chloride emulsion Em-22 and silver chloro-bromide emulsion Em-23 both having a grain size of 0.4 ⁇ m were prepared according to the preparation method described for Em-12 and Em-13 in Example 10.
  • Sodium thiosulfate was added to these emulsions as a sulfur sensitizing agent, and chloroauric acid was further added, then each emulsion was subjected to the chemical ripening step, and divided into two parts.
  • Sensitizing dye GS-1 was added to one part, and RS-1 was added to the other. Five minutes later, stabilizing agent ST-1 was added to both emulsions, thus terminating the chemical ripening step.
  • green-sensitive emulsion containing GS-1 and red-sensitive emulsion containing RS-1 were prepared.
  • a silver halide color photographic light-sensitive material was obtained.
  • the quantity of each chemical compound is represented in weight per 1 m2 of color photographic light-sensitive material in the following description:
  • the color paper thus prepared was subjected to an exposure process through a color negative and to the color developing process used in Example 10.
  • the exposure conditions were adjusted so that an optimum result was obtained for Sample 1401 or 1404.
  • the exposure condition adjusted for Sample 1401 was applied to Samples 1405 and 1404, and the condition adjusted for Sample 1404 was applied to Samples 1405 and 1406.
  • Color prints of Samples 1405 and 1406 equivalent to those of Samples 1401 and 1404 were obtained, however, the color print obtained from Sample 1402 was blueish.
  • the characteristic fluctuation caused by manufacturing silver halide photographic light-sensitive materials using emulsions containing silver chloride from 99.0 to 99.5 mol% was limited to a very small value, thus enabling color prints to be obtained without substantially changing the color developing conditions.

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Claims (10)

  1. Verfahren zur Herstellung eines lichtempfindlichen farbphotographischen Silberhalogenid-Aufzeichnungsmaterials mit einem Schichtträger und mindestens einer darauf aufgetragenen photographischen Schichtkomponente mit mindestens einer Silberhalogenidemulsionsschicht mit
    (a) Silberhalogenidkörnchen mit nicht weniger als 80 Mol-% Silberchlorid;
    (b) einer Goldverbindung in einer Menge von 5 x 10⁻⁷ bis 5 x 10⁻³ Mol/Mol des in der Silberhalogenidemulsionsschicht enthaltenen Silberhalogenids;
    (c) eines Schwefelsensibilisierungsmittels und
    (d) eines spektralen Sensibilisierungsfarbstoffs der Formel [I] in einer Menge von 5 x 10⁻⁶ bis 5 x 10⁻² Mol/Mol des in der Silberhalogenidemulsionsschicht enthaltenen Silberhalogenids:
    Figure imgb0060
     worin bedeuten:
    X₁, X₂, X₃ und X₄ unabhängig voneinander Wasserstoff, Halogen, Alkyl, Alkoxy, Aryl oder Hydroxy;
    R₁ und R₂ unabhängig voneinander gegebenenfalls substituiertes Alkyl;
    X⊖ ein Anion und
    n = 0 oder 1,
    wobei der Sensibilisierungsfarbstoff in die Emulsion nach Beendigung einer ersten Reifungsstufe und vor Beendigung einer zweiten Reifungsstufe eingearbeitet wird.
  2. Verfahren nach Anspruch 1, wobei die Silberhalogenidkörnchen 99,0 bis 99,9 Mol-% Silberchlorid enthalten.
  3. Verfahren nach Anspruch 1 oder 2, wobei die Silberhalogenidkörnchen mit 1 x 10⁻⁶ bis 1 x 10⁻⁴ Mol Goldverbindung pro Mol des in der Silberhalogenidemulsionsschicht enthaltenen Silberhalogenids sensibilisiert werden.
  4. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Silberhalogenidkörnchen mit 1 x 10⁻⁵ bis 1 x 10⁻³ Mol des Spektralsensibilisierungsfarbstoffs pro Mol des in der Silberhalogenidemulsionsschicht enthaltenen Silberhalogenids sensibilisiert werden.
  5. Verfahren nach einem der vorhergehenden Ansprüche, wobei mindestens eine der photographischen Schichtkomponenten eine Schwarz/Weiß-Entwicklerverbindung enthält.
  6. Verfahren nach Anspruch 5, wobei die Schwarz/Weiß-Entwicklerverbindung aus einem Dihydroxybenzol besteht.
  7. Verfahren nach einem der vorhergehenden Ansprüche, wobei die Silberhalogenidemulsionsschicht einen Gelbkuppler der Formel [Y]:
    Figure imgb0061
     worin bedeuten:
    R₂₁ ein Halogen oder Alkoxy;
    R₂₂ -NHCOR₂₃SO₂R₂₄, -COOR₂₄, -COOR₂₃COOR₂₄,
    Figure imgb0062
     oder
    Figure imgb0063
     mit R₂₃ gleich Alkylen, R₂₄ gleich einer Ballastgruppe und R₂₅ gleich Alkyl, Aralkyl oder Wasserstoff, und
    Z₂₁ eine bei der Reaktion mit einem Oxidationsprodukt einer Farbentwicklerverbindung abspaltbare Gruppe, enthält.
  8. Verfahren nach einem der vorhergehenden Ansprüche, wobei sämtliche vorhandenen Silberhalogenidemulsionsschichten Silberhalogenidkörnchen mit nicht weniger als 80 Mol-% Silberchlorid enthalten.
  9. Verfahren nach Anspruch 8, wobei der durchschnittliche Silberchloridgehalt der in jeder Silberhalogenidemulsionsschicht enthaltenen Silberhalogenidkörnchen nicht weniger als 95 Mol-% beträgt.
  10. Verfahren nach einem der vorhergehenden Ansprüche, wobei R₁ und R₂ unabhängig voneinander für unsubstituiertes Alkyl oder carboxy- oder sulfosubstituiertes Alkyl stehen.
EP87306813A 1986-07-31 1987-07-31 Farbphotoempfindliches Silberhalogenidmaterial für schnelle Behandlung Expired - Lifetime EP0255983B1 (de)

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AU591316B2 (en) * 1986-07-31 1989-11-30 Konishiroku Photo Industry Co., Ltd. Light-sensitive silver halide photographic material feasible for rapid processing
DE3889189T2 (de) * 1987-10-09 1994-09-01 Fuji Photo Film Co Ltd Farbphotographisches Silberhalogenidmaterial.
JPH087412B2 (ja) * 1988-10-03 1996-01-29 富士写真フイルム株式会社 カラー写真画像形成方法
US5672465A (en) * 1990-04-09 1997-09-30 Jp Laboratories, Inc. Polyethyleneimine binder complex films
US5389338A (en) * 1991-01-06 1995-02-14 Orgenics Ltd. Apparatus for dry chemical analysis of fluids
EP0512496B1 (de) * 1991-05-10 1995-12-20 Fuji Photo Film Co., Ltd. Photographisches Silberhalogenidmaterial
US5462843A (en) * 1992-04-06 1995-10-31 Agfa-Gevaert Ag Recording material for color photography
DE4211462A1 (de) * 1992-04-06 1993-10-07 Agfa Gevaert Ag Farbfotografisches Aufzeichnungsmaterial
US5389507A (en) * 1992-12-31 1995-02-14 Eastman Kodak Company Reversal elements with internal latent image forming core-shell emulsions

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US2624361A (en) * 1946-03-30 1953-01-06 Bendix Aviat Corp Valve for controlling fluid to a plurality of devices
US3128185A (en) * 1960-01-25 1964-04-07 Eastman Kodak Co Antifoggants for formaldehydehardened photographic layers
US3915715A (en) * 1970-08-13 1975-10-28 Eastman Kodak Co Silver halide photographic materials containing a high weight ratio of gold to sulfur sensitizers and a sensitizing methine dye
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US4225666A (en) * 1979-02-02 1980-09-30 Eastman Kodak Company Silver halide precipitation and methine dye spectral sensitization process and products thereof
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